Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetra-chloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane

ABSTRACT

The present disclosure relates to compositions comprising 2,3,3,3-tetrafluoropropene that may be useful as heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. Additionally, the present disclosure relates to compositions comprising 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane, which may be useful in processes to produce 2,3,3,3-tetrafluoropropene.

FIELD OF THE INVENTION

The present disclosure relates to the field of compositions which may beuseful as heat transfer compositions, aerosol propellants, foamingagents (blowing agents), solvents, cleaning agents, carrier fluids,displacement drying agents, buffing abrasion agents, polymerizationmedia, foaming agents for polyolefins and polyurethane, gaseousdielectrics, extinguishing agents, and fire suppression agents in liquidor gaseous form. In particular, the present disclosure relates tocompositions which may be useful as heat transfer compositions, such as2,3,3,3-tetrafluoropropene (HFO-1234yf, or 1234yf) or the compositionscomprising 1,1,1,2,3-pentafluoropropane (HFC-245eb, or 245eb) which areuseful in processes to produce HFO-1234yf.

BACKGROUND OF THE INVENTION

New environmental regulations have led to the need for new compositionsfor use in refrigeration, air-conditioning and heat pump apparatus. Lowglobal warming potential compounds are of particular interest.

SUMMARY OF THE INVENTION

Applicants have found that in preparing such new low global warmingpotential compounds, such as HFO-1234yf, that certain additionalcompounds are present in small amounts.

Therefore, in accordance with the present invention, there is provided acomposition comprising HFO-1234yf and at least one additional compoundselected from the group consisting of HCO-1250xf, HCC-260da, HCC-240aa,HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244 db,HFO-1234ze, HFC-245cb, HFC-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc,HCFC-241 db, HCFC-242dc, HCFC-1232xf, HCFO-1231xf, and HCFO-1233yf. Thecomposition may contain less than about 1 weight percent of the at leastone additional compound, based on the total weight of the composition.

In addition, in accordance with the present invention, there is provideda composition comprising HCO-1230xa and at least one additional compoundselected from the group consisting of propylene, HCO-1260zf, HCC-260da,HCC-260 db, HCO-1250xf, HCC-250aa, and HCC-240aa.

In addition, in accordance with the present invention, there is provideda composition comprising HCFO-1233xf and at least one additionalcompound selected from the group consisting of propylene, HCO-1260zf,HCC-260da, HCC-260 db, HCO-1250xf, HCC-250aa, HCC-240aa, HCO-1230xa,HFC-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1233yf,HCFO-1232xf, HCFC-1231xf, HCFC-241 db, and HCFC-242dc.

In addition, in accordance with the present invention, there is provideda composition comprising HCFC-244bb and at least one additional compoundselected from the group consisting of propylene, HCO-1250xf, HCC-260da,HCC-260 db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HFO-1243zf, HCFO-1223az,HCFC-1224zb, HFO-1225zc, HCFC-241 db, HCFC-242dc, HCFO-1232xf,HCFO-1231xf, and HCFC-1233yf.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a reaction sequence useful for formation of compositions ofthe present invention.

DETAILED DESCRIPTION Compositions

HFO-1234yf (2,3,3,3-tetrafluoropropene) has been suggested for use as arefrigerant, heat transfer fluid, aerosol propellant, foam expansionagent, among other uses. It has also, advantageously, been found thatHFO-1234yf has a low global warming potential (GWP) as reported by V. C.Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007,volume 9, pages 1-13. Thus, HFO-1234yf is a good candidate for replacingthe higher GWP saturated HFC refrigerants.

In one embodiment, the present disclosure provides a compositioncomprising HFO-1234yf and at least one additional compound selected fromthe group consisting of HCO-1250xf, HCC-260da, HCC-260 db, HCC-240aa,HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244 db,HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc,HCFC-241 db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf.

The compositions of the present invention may comprise HFO-1234yf andone additional compound, or two additional compounds, or three or moreadditional compounds.

In another embodiment, the compositions of the present inventioncomprise HFO-1234yf and HCFO-1232xf.

In another embodiment, the compositions of the present inventioncomprise HFO-1234yf and at least one compound selected from HCFC-243 db,HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241 db.

In another embodiment, the compositions of the present inventioncomprise at least one compound selected from the group consisting ofHCFC-243 db and HFC-245fa.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HFO-1234yf ranges from greater than zero weightpercent to less than 1 weight percent, based on the total weight of thecomposition. In another embodiment, the total amount of additionalcompound(s) ranges from greater than zero weight percent to less than0.5 weight percent, based on the total weight of the composition.

In one embodiment, the compositions comprising HFO-1234yf and othercompounds may further comprise a specific tracer compound, such asHFC-245cb. In this embodiment, the HFC-245cb tracer may be present at aconcentration from about 1 part per million (ppm) to about 1000 ppm inthe composition. In another embodiment, the HFC-245cb tracer may bepresent at a concentration from about 1 ppm to about 500 ppm.Alternatively, the HFC-245cb tracer may be present at a concentrationfrom about 10 ppm to about 300 ppm.

The compositions disclosed herein comprising HFO-1234yf are useful aslow global warming potential (GWP) heat transfer compositions, aerosolpropellant, foaming agents, blowing agents, solvents, cleaning agents,carrier fluids, displacement drying agents, buffing abrasion agents,polymerization media, expansion agents for polyolefins and polyurethane,gaseous dielectrics, extinguishing agents, and fire suppression agentsin liquid or gaseous form. The disclosed compositions can act as aworking fluid used to carry heat from a heat source to a heat sink. Suchheat transfer compositions may also be useful as a refrigerant in acycle wherein the fluid undergoes a phase change; that is, from a liquidto a gas and back or vice versa.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

As used herein, mobile refrigeration apparatus, mobile air conditioningor mobile heating apparatus refers to any refrigeration, airconditioner, or heating apparatus incorporated into a transportationunit for the road, rail, sea or air. In addition, mobile refrigerationor air conditioner units, include those apparatus that are independentof any moving carrier and are known as “intermodal” systems. Suchintermodal systems include “containers’ (combined sea/land transport) aswell as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems associatedwithin or attached to buildings of any variety. These stationaryapplications may be stationary air conditioning and heat pumps(including but not limited to chillers, high temperature heat pumps,residential, commercial or industrial air conditioning systems, andincluding window, ductless, ducted, packaged terminal, chillers, andthose exterior but connected to the building such as rooftop systems).In stationary refrigeration applications, the disclosed compositions maybe useful in high temperature, medium temperature, and/or lowtemperature refrigeration equipment including commercial, industrial orresidential refrigerators and freezers, ice machines, self-containedcoolers and freezers, flooded evaporator chillers, direct expansionchillers, walk-in and reach-in coolers and freezers, and combinationsystems. In some embodiments, the disclosed compositions may be used insupermarket refrigerator and/or freezer systems.

The compounds making up the disclosed compositions are defined in Table1.

TABLE 1 Code Formula Name Propylene HCO-1260zf CH₂═CHCH₂Cl3-chloropropene HCO-1250xf CH₂═CClCH₂Cl 2,3-dichloropropene HCC-260daCH₂ClCHClCH₂Cl 1,2,3-trichloropropane HCC-260db CH₃CHClCHCl₂1,1,2-trichloropropane HCC-250aa CH₂ClCCl₂CH₂Cl1,2,2,3-tetrachloropropane HCC-240aa CHCl₂CCl₂CH₂Cl1,1,2,2,3-pentachloropropane HCO-1230xa CCl₂═CClCH₂Cl1,1,2,3-tetrachloropropene HCFO-1233xf CF₃CCl═CH₂2-chloro-3,3,3-trifluoropropene HCFO-1233zd CF₃CH═CHCl1-chloro-3,3,3-trifluoropropene HCFC-244bb CF₃CFClCH₃2-chloro-1,1,1,2-tetrafluoropropane HCFC-244db CF₃CHClCH₂F2-chloro-1,1,1,3-tetrafluoropropane HFO-1234ze CF₃CH═CHF1,3,3,3-tetrafluoropropene HFC-245cb CF₃CF₂CH₃1,1,1,2,2-pentafluoropropane HFO-1243zf CF₃CH═CH₂ 3,3,3-trifluoropropeneHCFO-1223za CF₃CH═CCl₂ 1,1-dichloro-3,3,3-trifluoropropene HCFO-1224zbCF₃CH═CClF 1-chloro-1,3,3,3-tetrafluoropropene HFO-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoropropene HCFC-241db CCl₂FCHClCH₂Cl1-chloro-1,1,2,3-tetrafluoropropane HCFC-242dc CClF₂CHClCH₂Cl1,1-difluoro-1,2,3-trichloropropane HCFO-1232xf CClF₂CCl═CH₂2,3-dichloro-3,3-difluoropropene HCFO-1231xf CCl₂FCCl═CH₂2,3,3-trichloro-3-fluoropropene HCFO-1233yf CClF₂CF═CH₂3-chloro-2,3,3-trifluoropropene HCFC-243db CF₃CHClCH₂Cl2,3-dichloro-1,1,1-trifluoro- propane HFC-245fa CF₃CH₂CHF₂1,1,1,3,3-pentafluoropropane

HCFO-1233xf, HCFC-244bb, and many other compounds as listed in Table 1are available from specialty chemical manufacturers, including SynQuestLaboratories, Inc. (Alachua, Fla., U.S.A.) or may be made by methodsknown in the art. For instance, HCFO-1233xf, and HCFC-244bb may beprepared by non-catalytic chlorination of HFO-1243zf, as described inInternational Patent Application Publication No. WO20081054782,published May 8, 2008. Also, HCFO-1233xf and HCFC-244bb may be preparedby catalytic fluorination of HCFC-243 db as described in InternationalPatent Application Publication No. WO2008/054781, published May 8, 2008.The additional compounds present in each disclosed composition willdepend upon the method of manufacture.

Alternatively, HCO-1230xa can be produced from 1,2,3-trichloropropane asdescribed in US2007/0197842 A1. Additionally, disclosed inUS2007/0197842 is the reaction of HCO-1230xa with HF in the presence ofcatalyst in the vapor phase to form HCFO-1233xf. Alternatively,HCFO-1233xf may also be produced by fluorination of1,1,2,3-tetrachloropropene, (HCO-1230xa) with further fluorinationforming HCFC-244bb and then dehydrochlorination forming HFO-1234yf, asdescribed in US2009/0240090.

Certain of the compounds listed in Table 1 may exist in more than oneisomer, in particular HFO-1234ze, HCFO-1233zd, and HCFO-1224zb. Forinstance, HFO-1234ze may exist as the E-isomer or Z-isomer. As usedherein HFO-1234ze is intended to refer to either of the E-isomer, theZ-isomer or any mixtures of these isomers. As used herein HCFO-1233zd isintended to refer to either of the E-isomer, the Z-isomer or anymixtures of these isomers. As used herein HFO-1224zb is intended torefer to either of the E-isomer, the Z-isomer or any mixtures of theseisomers.

In addition, in accordance with the present invention, there is provideda composition comprising HCO-1230xa and at least one additional compoundselected from the group consisting of propylene, HCO-1260zf, HCC-260da,HCC-260 db, HCO-1250xf, HCC-250aa, and HCC-240aa.

In another embodiment, the compositions of the present inventioncomprise HCO-1230xa and HCC-240aa. And in another embodiment, thecompositions of the present invention may comprise HCO-1230xa,HCC-240aa, and at least one compound selected from the group consistingof HCC-250aa and HCC-260da.

In addition, in accordance with the present invention, there is provideda composition comprising HCFO-1233xf and at least one additionalcompound selected from the group consisting of propylene, HCO-1260zf,HCC-260da, HCC-260 db, HCO-1250xf, HCC-250aa, HCC-240aa, HCO-1230xa,HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1233yf,HCFO-1232xf, HCFC-1231xf, HCFC-241 db, and HCFC-242dc.

In another embodiment, the compositions of the present inventioncomprise HCO-1230xa and HCFO-1232xf. And in another embodiment thecompositions of the present invention comprise, HCO-1230xa, HCFO-1232xfand HCFO-1231xf.

In addition, in accordance with the present invention, there is provideda composition comprising HCFC-244bb and at least one additional compoundselected from the group consisting of propylene, HCO-1250xf, HCC-260da,HCC-260 db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HFO-1243zf, HCFO-1223az,HCFO-1224zb, HFO-1225zc, HCFC-241 db, HCFC-242dc, HCFO-1232xf,HCFO-1231xf, and HCFC-1233yf.

In another embodiment, the compositions of the present inventioncomprising HCFC-244bb may further comprise at least one compoundselected from the group consisting of HCFC-243 db and HFC-245fa.

The series of reactions that may form the compositions of the presentinvention are shown in FIG. 1. The sequence of steps begins with thechorination of propylene by reaction with chlorine, Cl₂ to form allylchloride or HCO-1260zf (CH₂═CHCH₂Cl). The next step involves furtherchlorination in the presence of Cl₂ to product HCC-260 db(CH₂ClCHClCH₂Cl). Reaction of HCC-260 db with aqueous NaOH (or othercaustic solution) forms HCO-1250xf (CH₂═CClCH₂Cl). And reaction ofHCO-1250xf with chlorine, Cl₂ produces HCC-250aa (CH₂ClCC₂H₂CH₂, or1,2,2,3-tetrachloropropane). Further chlorination with Cl₂ will produceHCC-240da (CHCl₂CCl₂CH₂Cl). Reaction of HCC-240da with aqueous NaOH (orother caustic solution) will form HCO-1230xa (CCl₂═CClCH₂Cl).

In another embodiment, any of the compositions as described previouslymay additionally comprise hydrogen fluoride (HF), due to the presence ofHF as either a reactant or a by-product of the reaction chemistry toproduce each composition.

Of note are compositions which are free of HCl, compositions which arefree of HF and compositions which are free of both HCl and HF. Ofparticular note are compositions which are acid free. Acids can beremoved by processes known in the art such as distillation and water orcaustic washing.

Fluorination of HCO-1230xa

The HCO-1230xa may be fluorinated by reaction with hydrogen fluoride(HF) in the presence of a catalyst to produce HCFO-1233xf. This reactionis shown in FIG. 1.

The fluorochlorination reaction may be carried out in the liquid orvapor phase. For liquid phase embodiments of the invention, the reactionof HCO-1230xa with HF may be conducted in a liquid-phase reactoroperating in batch, semi-batch, semi-continuous, or continuous modes. Inthe batch mode, HCO-1230xa and HF are combined in an autoclave or othersuitable reaction vessel and heated to the desired temperature.

In one embodiment, this reaction is carried out in semi-batch mode byfeeding HCO-1230xa to a liquid-phase reactor containing HF. In anotherembodiment, HF may be fed to a liquid-phase reactor containing a mixtureof HCO-1230xa and reaction products formed by reacting HF andHCO-1230xa. In another embodiment of the liquid-phase process, HF andHCO-1230xa may be fed concurrently in the desired stoichiometric ratioto the reactor containing a mixture of HF and reaction products formedby reacting HF and HCO-1230xa.

Suitable temperatures for the reaction of HF with HCO-1230xa in theliquid-phase reactor are, in one embodiment, from about 80° C. to about180° C., and in another embodiment, from about 100° C. to about 150° C.Higher temperatures typically result in greater conversion of theHCO-1230xa.

A suitable molar ratio of HF to total amount of HCO-1230xa fed to theliquid-phase reactor is, in one embodiment, at least stoichiometric(about 3:1, HF to HCO-1230xa) and in another embodiment, is from about5:1 to about 100:1. Of note are embodiments wherein the molar ratio ofHF to HFO-1243zf is from about 8:1 to about 50:1.

The reactor pressure in the liquid-phase process is not critical and inbatch reactions is usually the autogenous pressure of the system at thereaction temperature. The pressure of the system increases as hydrogenchloride is formed by replacement of hydrogen substituents by chlorine,and by replacement of chlorine substituents by fluorine in the startingmaterials and intermediate reaction products. In a continuous process itis possible to set the pressure of the reactor in such a way that thelower boiling products of the reaction are vented from the reactor,optionally through a packed column or condenser. In this manner, higherboiling intermediates remain in the reactor and the volatile productsare removed. Typical reactor pressures are from about 20 psig (239 kPa)to about 1,000 psig (6,994 kPa).

In some embodiments, in which the reaction is conducted using aliquid-phase process, catalysts which may be used include carbon, AIF₃,BF₃, FeCl_(3-a)F_(a) (where a=0 to 3), FeX₃ supported on carbon,SbCl_(3-a)F_(a), AsF₃, MCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, Ta,or Mo), and M′Cl_(4-c)F_(c) (where c=0 to 4, and M′=Sn, Ti, Zr, or Hf).In another embodiment, catalysts for the liquid phase process areMCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, or Ta).

In another embodiment, the reaction of HF with HCO-1230xa is carried outin the vapor phase. Typically a heated reactor is used. A number ofreactor configurations are possible including horizontal or verticalorientation of the reactor as well as the sequence of reaction of theHCO-1230xa with HF. In one embodiment of the invention, the HCO-1230xamay be initially vaporized and fed to the reactor as a gas.

Suitable temperatures for the vapor-phase reaction are from about 120°C. to about 500° C. Higher temperatures result in greater conversion ofHCO-1230xa and higher degrees of fluorination and halogenation in theconverted compounds.

Suitable reactor pressures for the vapor-phase reactor may be from about1 to about 30 atmospheres. A pressure of about 15 to about 25atmospheres may be advantageously employed to facilitate separation ofHCl from other reaction products, and the suitable reaction time mayvary from about 1 to about 120 seconds, preferably from about 5 to about60 seconds.

The molar ratio of HF to the total amount of HCO-1230xa for thevapor-phase reaction is, in one embodiment, from about thestoichiometric ratio of HF to the total amount of HCO-1230xa (3:1 HF toHCO-1230xa) to about 50:1 and, in another embodiment, from about 10:1 toabout 30:1.

In one embodiment, a catalyst is used in the reaction zone for thevapor-phase reaction of HF with (3:1 HF to HCO-1230xa).Chlorofluorination catalysts which may be used in the vapor phasereaction include carbon; graphite; alumina; fluorided alumina; aluminumfluoride; alumina supported on carbon; aluminum fluoride supported oncarbon; fluorided alumina supported on carbon; magnesium fluoridesupported on aluminum fluoride; metals (including elemental metals,metal oxides, metal halides, and/or other metal salts); metals supportedon aluminum fluoride; metals supported on fluorided alumina; metalssupported on alumina; and metals supported on carbon; mixtures ofmetals.

Suitable metals for use as catalysts (optionally supported on alumina,aluminum fluoride, fluorided alumina, or carbon) include chromium, iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium,zirconium, and hafnium, copper, silver, gold, zinc, and/or metals havingan atomic number of 58 through 71 (i.e., the lanthanide metals). In oneembodiment, when used on a support, the total metal content of thecatalyst will be from about 0.1 to about 20 percent by weight based onthe total weight of the catalyst; in another embodiment from about 0.1to about percent by weight based on the total weight of the catalyst.

Suitable chlorofluorination catalysts for the vapor-phase reactionsinclude chromium-containing catalysts including chromium(III) oxide(Cr₂O₃); Cr₂O₃ with other metals such as magnesium halides or zinchalides supported on Cr₂O₃; chromium(III) halides supported on carbon;mixtures of chromium and magnesium (including elemental metals, metaloxides, metal halides, and/or other metal salts) optionally supported ongraphite; and mixtures of chromium and other metals (including elementalmetals, metal oxides, metal halides, and/or other metal salts)optionally supported on graphite, alumina, or aluminum halides such asaluminum fluoride.

Chromium-containing catalysts are well known in the art. They may beprepared by either precipitation methods or impregnation methods asgenerally described by Satterfield on pages 87-112 in HeterogeneousCatalysis in Industrial Practice, 2^(nd) edition (McGraw-Hill, New York,1991).

Of note are chlorofluorination catalysts that comprise at least onechromium-containing component selected from the group consisting ofcrystalline alpha-chromium oxide where from about 0.05 atom % to about 6atom % of the chromium atoms in the alpha-chromium oxide lattice arereplaced by trivalent cobalt atoms, and crystalline alpha-chromium oxidewhere from about 0.05 atom % to about 6 atom % of the chromium atoms inthe alpha-chromium oxide lattice are replaced by trivalent cobalt atomswhich has been treated with a fluorinating agent. These catalysts,including their preparation, have been disclosed in U.S. PatentApplication Publication US2005/0228202.

In another embodiment, the vapor phase catalyst for reaction ofHCO-1230xa with HF may be a catalyst composition comprising Cr₂O₃prepared by pyrolysis of (NH₄)₂Cr₂O₇ as described in U.S. Pat. No.5,036,036.

Optionally, the metal-containing catalysts described above can bepretreated with HF. This pretreatment can be accomplished, for example,by placing the metal-containing catalyst in a suitable container, andthereafter, passing HF over the metal-containing catalyst. In oneembodiment, such container can be the reactor used to perform thechlorofluorination reaction. In one embodiment, the pretreatment time isfrom about 15 to about 300 minutes, and the pretreatment temperature isfrom about 200° C. to about 450° C.

Fluorination of HCFO-1233xf

In some embodiments, HCFO-1233xf may be used to make HCFC-HCFC-244bb,and/or HFO-1234yf by fluorination. These reactions are shown in FIG. 1.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in the liquid phase. In another embodiment, the reaction maybe carried out in the vapor phase.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in batch mode. In another embodiment, the reaction may becarried out in a continuous mode.

In one embodiment, a liquid phase reaction of HCFO-1233xf to HCFC-244bbmay be carried out in the presence of a catalyst. In one embodiment, thecatalyst may be a Lewis acid catalyst. In one embodiment, the catalystmay be a metal-halide catalyst. In another embodiment, the catalyst maybe at least one catalyst selected from the group consisting of antimonyhalides, tin halides, thallium halides, iron halides and combinations oftwo or more thereof. In another embodiment, the catalysts may be atleast one catalyst selected from antimony pentachloride (SbCl₅),antimony trichloride (SbCl₃), antimony pentafluoride (SbF₅), tintetrachloride (SnCl₄), titanium tetrachloride (TiCl₄), iron trichloride(FeCl₃, and combinations thereof. In some embodiments, the reaction maybe carried out with any known fluorination catalyst for liquid phasereactions.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in the absence of catalyst.

In one embodiment, a vapor phase reaction of HCFO-1233xf to HCFC-244bbmay be carried out in the presence of a catalyst. In one embodiment, thereaction is carried out in the presence of a chromium-based catalyst, aniron-based catalyst, or combinations thereof. In one embodiment, thechromium based catalyst is a chromium oxide (e.g. Cr₂O₃). In oneembodiment, the iron-based catalyst may be FeCl₃ on carbon.

In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bbis carried out in the absence of catalyst.

Dehydrochlorination of HCFC-244bb

In some embodiments, dehydrochlorination of HCFC-244bb is used toprepare HFO-1234yf.

In one embodiment, dehydrochlorination of HCFC-244bb to HFO-1234yf iscarried out in the vapor phase.

In one embodiment, vapor phase dehydrochlorination is carried out in thepresence of catalyst. In one embodiment, the catalyst is selected fromcarbon and/or metal based catalysts. In one embodiment, the catalyst maybe selected from an activated carbon, a nickel-based catalyst, apalladium based catalyst, or any combination of these catalysts.

In one embodiment, the catalyst may be selected from the groupconsisting of Ni-mesh, palladium on carbon, palladium on aluminum oxide,or combinations thereof.

In one embodiment, the catalyzed vapor phase dehydrochlorination iscarried out at a temperature from about 200 to 600° C. In anotherembodiment, the catalytic vapor phase dehydrochlorination is carried outat a temperature from about 250 to 500° C. The reaction pressure isabout from 0 to 150 psi.

In another embodiment, HFO-1234yf is prepared by thermaldehydrochlorination of HCFC-244bb. In one embodiment, this reactionoccurs in the absence of a catalyst. In one embodiment, HCFC-244bb isintroduced into a reaction vessel which temperature is maintained at atemperature high enough to effect the thermal dehydrochlorination ofHCFC-244bb. In one embodiment, the temperature is high enough to effectthe thermal dehydrochlorination of HCFC-244bb to a percent conversion ofat least 50%. In another embodiment, the temperature is high enough toeffect the thermal dehydrochlorination of HCFC-244bb to a percentconversion of at least 65%. In yet another embodiment, the temperatureis high enough to effect the thermal dehydrochlorination of HCFC-244bbto a percent conversion of at least 80%. In yet another embodiment, thetemperature is high enough to effect the thermal dehydrochlorination ofHCFC-244bb to a percent conversion of at least 70% for at least 12 hoursof continuous operation.

In one embodiment, HCFC-244bb is introduced into a reaction vessel intoa reaction vessel which temperature is maintained at a temperature inthe range of from about 500° C. to about 700° C. In another embodiment,the temperature of the reaction vessel is maintained in the range fromabout 500° C. to about 650° C. In yet another embodiment, thetemperature of the reaction vessel is maintained at a temperature highenough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with aselectivity of 80% or greater. In yet another embodiment, thetemperature of the reaction vessel is maintained at a temperature highenough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with aselectivity of 85% or greater.

In one embodiment, for either the catalyzed or non-catalyticdehydrochlorination reaction, the reaction zone is a reaction vesselcomprised of materials which are resistant to corrosion. In oneembodiment, these materials comprise alloys, such as nickel-based alloyssuch as Hastelloy®, nickel-chromium alloys commercially available fromSpecial Metals Corp. under the trademark Inconel® (hereinafter“Inconel®”) or nickel-copper alloys commercially available from SpecialMetals Corp. (New Hartford, N.Y.) under the trademark Monel®, or vesselshaving fluoropolymers linings.

In one embodiment, the HCFC-244bb is preheated in a vaporizer to atemperature of from about 30° C. to about 100° C. In another embodiment,the HCFC-244bb is preheated in a vaporizer to a temperature of fromabout 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas forHCFC-244bb. In one embodiment, the carrier gas is selected is nitrogen,argon, helium or carbon dioxide.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following specific embodiments are, therefore, to beconstrued as merely illustrative, and do not constrain the remainder ofthe disclosure in any way whatsoever.

Utility

The compositions disclosed herein comprising HFO-1234yf are useful aslow global warming potential (GWP) heat transfer compositions, aerosolpropellant, foam expansion agents (also known as foaming agents orblowing agents), solvents, cleaning agents, carrier fluids, displacementdrying agents, buffing abrasion agents, polymerization media, foamingagents for polyolefins and polyurethane, gaseous dielectrics,extinguishing agents, and fire suppression agents in liquid or gaseousform. The disclosed compositions can act as a working fluid used tocarry heat from a heat source to a heat sink. Such heat transfercompositions may also be useful as a refrigerant in a cycle wherein thefluid undergoes a phase change; that is, from a liquid to a gas and backor vice versa.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

In one embodiment, the compositions comprising HFO-1234yf are useful inmobile heat transfer systems, including refrigeration, air conditioning,or heat pump systems or apparatus. In another embodiment, thecompositions are useful in stationary heat transfer systems, includingrefrigeration, air conditioning, or heat pump systems or apparatus.

As used herein, mobile heat transfer systems refers to anyrefrigeration, air conditioner, or heating apparatus incorporated into atransportation unit for the road, rail, sea or air. In addition, mobilerefrigeration or air conditioner units, include those apparatus that areindependent of any moving carrier and are known as “intermodal” systems.Such intermodal systems include “containers’ (combined sea/landtransport) as well as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps (including but not limited to chillers, hightemperature heat pumps, residential, commercial or industrial airconditioning systems, and including window, ductless, ducted, packagedterminal, chillers, and those exterior but connected to the buildingsuch as rooftop systems). In stationary refrigeration applications, thedisclosed compositions may be useful in high temperature, mediumtemperature and/or low temperature refrigeration equipment includingcommercial, industrial or residential refrigerators and freezers, icemachines, self-contained coolers and freezers, flooded evaporatorchillers, direct expansion chillers, walk-in and reach-in coolers andfreezers, and combination systems. In some embodiments, the disclosedcompositions may be used in supermarket refrigerator systems.

Therefore in accordance with the present invention, the compositions asdisclosed herein containing HFO-1234yf may be useful in methods forproducing cooling, producing heat, and transferring heat.

The compositions disclosed herein may be useful as low global warmingpotential (GWP) replacements for currently used refrigerants, includingbut not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22(or HCFC-22, chlorodifluoromethane), R12 (CFC-12,dichlorodifluoromethane); R407c (ASHRAE designation for a blend of 52weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23weight percent R32 (difluoromethane)); R410A (ASHRAE designation for ablend of 50 weight percent R125 and 50 weight percent R32); and R404A(ASHRAE designation for a blend of 44 weight percent R125, 52 weightpercent R143a (1,1,1-trifluoroethane), and 4.0 weight percent R134a),among others.

In many applications, some embodiments of the present compositionscomprising HFO-1234yf are useful as refrigerants and provide at leastcomparable cooling performance (meaning cooling capacity and energyefficiency) as the refrigerant for which a replacement is being sought.

In another embodiment is provided a method for recharging a heattransfer system that contains a refrigerant to be replaced and alubricant, said method comprising removing the refrigerant to bereplaced from the heat transfer system while retaining a substantialportion of the lubricant in said system and introducing one of thepresent compositions comprising HFO-1234yf to the heat transfer system.

In another embodiment, a heat exchange system containing any of thepresent compositions comprising HFO-1234yf is provided, wherein saidsystem is selected from the group consisting of air conditioners,freezers, refrigerators, heat pumps, water chillers, flooded evaporatorchillers, direct expansion chillers, walk-in coolers, heat pumps, mobilerefrigerators, mobile air conditioning units, and systems havingcombinations thereof. Additionally, the compositions comprisingHFO-1234yf may be useful in secondary loop systems wherein thesecompositions serve as the primary refrigerant thus providing cooling toa secondary heat transfer fluid that thereby cools a remote location.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator, by withdrawing heat from theenvironment, at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

In one embodiment, there is provided a heat transfer system containingany of the present compositions comprising HFO-1234yf. In anotherembodiment is disclosed a refrigeration, air-conditioning or heat pumpapparatus containing any of the present compositions comprisingHFO-1234yf. In another embodiment, is disclosed a stationaryrefrigeration or air-conditioning apparatus containing any of thepresent compositions comprising HFO-1234yf. In yet another embodiment isdisclosed a mobile refrigeration or air conditioning apparatuscontaining a composition as disclosed herein.

In another embodiment, a method is provided for producing coolingcomprising evaporating any of the present compositions comprisingHFO-1234yf in the vicinity of a body to be cooled, and thereaftercondensing said composition.

In another embodiment, a method is provided for producing heatcomprising condensing any of the present compositions comprisingHFO-1234yf in the vicinity of a body to be heated, and thereafterevaporating said compositions.

In another embodiment, disclosed is a method of using the presentcompositions comprising HFO-1234yf as a heat transfer fluid composition.The method comprises transporting said composition from a heat source toa heat sink.

In another embodiment, the present invention relates to foam expansionagent compositions comprising HFO-1234yf for use in preparing foams. Inother embodiments the invention provides foamable compositions, andpreferably thermoset (like polyurethane, polyisocyanurate, or phenolic)foam compositions, and thermoplastic (like polystyrene, polyethylene, orpolypropylene) foam compositions and method of preparing foams. In suchfoam embodiments, one or more of the present compositions comprisingHFO-1234yf are included as a foam expansion agent in foamablecompositions, which composition preferably includes one or moreadditional components capable of reacting and/or mixing and foamingunder the proper conditions to form a foam or cellular structure.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition a compositioncomprising HFO-1234yf of the present invention; and (b) processing thefoamable composition under conditions effective to form a foam.

Another embodiment of the present invention relates to the use of thecompositions of the present invention comprising HFO-1234yf aspropellants in sprayable compositions. Additionally, the presentinvention relates to a sprayable compositions comprising HFO-1234yf. Theactive ingredient to be sprayed together with inert ingredients,solvents and other materials may also be present in a sprayablecomposition. In one embodiment, a sprayable composition is an aerosol.The present compositions can be used to formulate a variety ofindustrial aerosols or other sprayable compositions such as contactcleaners, dusters, lubricant sprays, mold release sprays, insecticides,and the like, and consumer aerosols such as personal care products (suchas, e.g., hair sprays, deodorants, and perfumes), household products(such as, e.g., waxes, polishes, pan sprays, room fresheners, andhousehold insecticides), and automotive products (such as, e.g.,cleaners and polishers), as well as medicinal materials such asanti-asthma and anti-halitosis medications. Examples of this includesmetered dose inhalers (MDIs) for the treatment of asthma and otherchronic obstructive pulmonary diseases and for delivery of medicamentsto accessible mucous membranes or intranasally

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a composition of the presentinvention comprising HFO-1234yf to a formulation, including active,ingredients in an aerosol container, wherein said composition functionsas a propellant. Additionally, the present invention further relates toa process for producing aerosol products comprising the step of adding acomposition of the present invention comprising HFO-1234yf to a barriertype aerosol package (like a bag-in-a-can or piston can) wherein saidcomposition is kept separated from other formulation ingredients in anaerosol container, and wherein said composition functions as apropellant. Additionally, the present invention further relates to aprocess for producing aerosol products comprising the step of addingonly a composition of the present invention comprising HFO-1234yf to anaerosol package, wherein said composition functions as the activeingredient (e.g., a duster, or a cooling or freezing spray).

The compositions disclosed herein comprising HCO-1230xa, HCFO-1233xf,and HCFC-244bb are useful in methods to prepare HFO-1234yf as describedpreviously herein.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following specific embodiments are, therefore, to beconstrued as merely illustrative, and do not constrain the remainder ofthe disclosure in any way whatsoever.

EXAMPLES General Procedure for Product Analysis

The following general procedure is illustrative of the method used foranalyzing the products of fluorination reactions. Part of the totalreactor effluent was sampled on-line for organic product analysis usinga gas chromatograph equipped with a mass selective detector (GC/MS). Thegas chromatography utilized a 20 ft. (6.1 m) long×⅛ in. (0.32 cm)diameter tube containing perfluorinated polyether sold under thetrademark Krytox® by E. I. du Pont de Nemours and Company (hereinafter“DuPont”) of Wilmington, Del. on an inert carbon support. The heliumflow was 30 mL/min (5.0×10⁻⁷ m³/sec). Gas chromatographic conditionswere 60° C. for an initial hold period of three minutes followed bytemperature programming to 200° C. at a rate of 6° C./minute.

Example 1 Fluorination of HCFO-1233xf to HCFC-244bb

The contents of a small PTFE vial containing 20 grams of viscous SbF₅were poured into a dry 400 mL Hastelloy® shaker tube. The tube wasclosed and was pressurized with nitrogen for leak testing. The shakertube was then cooled to less than −40° C. with dry ice, slowly vented,and then evacuated. 75 grams (3.75-moles) of anhydrous HF was condensedinto the shaker tube followed by 165 grams (1.26-moles) of HCFO-1233xf.The shaker tube was placed in a barricade and shaking was started.

The shaker tube was agitated at ambient temperature (˜20-23° C.) and thepressure was 21 to 25 psig. After 2 hours, shaking was stopped and 150mL of water was carefully pumped into the shaker tube. The tube was leftovernight and then cooled to 0 to 5° C. in an ice bath beforedepressurization and transferring the contents to a plastic container.The container was kept on ice.

The container contents were poured into a polypropylene separatoryfunnel containing some ice. The lower organic layer was light amber inappearance. The organic layer was separated into a media bottle made ofa glass sold under the trademark of Pyrex® by Corning (Lowell, Mass.)(hereinafter “Pyrex®”) containing ˜50-mL of 4 molar (pH 7) phosphatebuffer and ice (˜100-mL). The organic layer was again separated andpoured into a dry Pyrex® media bottle containing a small amount ofanhydrous magnesium sulfate. Crude yield was 164.3 grams (about 120-mL,86%).

GC/MS of the crude material showed that it was mostly HCFC-244bb. Othercomponents included 0.16% 1233xf, and other byproducts totaling 12.2%.

Example 2 Fluorination of HCFO-1233xf to HCFC-244bb

The contents of a small PTFE vial containing 20 grams of viscous SbF₅were poured into a dry 400-mL Hastelloy® shaker tube. The tube wasclosed and was pressurized with nitrogen for leak testing. The shakertube was then cooled to less than −40° C. with dry ice, slowly vented,and then evacuated. 53 grams (2.65 moles) of anhydrous HF wastransferred into the shaker tube followed by 227 grams (1.74 moles) ofHCFO-1233xf was condensed into the chilled shaker tube. The shaker tubewas placed in the barricade and shaking was started.

The shaker tube was agitated at ambient temperature (˜18-21° C.) and thepressure was 16 to 20 psig. After 2 hours, shaking was stopped and 100mL of water was carefully pumped into the shaker tube. The tube was leftovernight and cooled to 0 to 5° C. in an ice bath before venting andtransferring the contents to a plastic container. The container was kepton ice.

The container contents were poured into a polypropylene separatoryfunnel containing some ice. The lower organic layer was light amber inappearance. The organic layer was separated into a Pyrex® media bottlecontaining about 50 mL of 4 molar (pH 7) phosphate buffer and ice(˜100-mL). The organic layer was again separated and poured into a dryPyrex® media bottle containing a small amount of anhydrous magnesiumsulfate. Crude yield was 238.8 grams (about 170-mL, 91%).

GC/MS of the crude material indicated that it was mostly HCFC-244bb.Other components included 0.11% HFC-245cb, 0.10% HFC-245eb, 0.26%HCFO-1233xf, and other byproducts totaling 9.7%.

Example 3

Example 3 demonstrates the conversion of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf(2,3,3,3-tetrafluoropropene) in the absence of a catalyst.

An empty Inconel® tube (½ inch OD) with a heated zone of about 12 incheswas heated to a temperature between 500° C. and 626° C., and HFC-244bbwas fed at 0.52 mL/hour through a vaporizer set at 40° C. using a N₂sweep of 2.4 sccm (4.0×10⁻⁸ m³). The reactor effluent was analyzed usingan on-line GCMS, with the results being reported in mole percent.

TABLE 2 Temp., Mole Percent ° C. 1234yf 244bb 1233xf Other 500 14.2 82.61.2 2.0 550 57.0 35.4 1.2 6.4 574 77.0 13.0 1.4 8.6 603 85.0 1.3 0.713.0 626 82.5 0.2 1.4 15.9

Example 4

Example 4 demonstrates the conversion of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf(2,3,3,3-tetrafluoropropane) in the absence of a catalyst.

An empty Inconel® tube (½ inch OD) with a heated zone of about 12 incheswas heated to 575° C., and HFC-244bb was fed at 0.35 mL/hour through avaporizer set at 40° C. using a N₂ sweep of 3.6 sccm (6.0×10⁻¹ m³). Thereactor was operated for a total of 19 hours continuously, and sampleswere taken periodically and analyzed to determine % conversion ofHFC-244bb, and selectivity to HFO-1234yf. The reactor effluent wasanalyzed using an on-line GCMS, and the data in Table 6 below is anaverage of at least two on-line injections at a given condition; thepercentages are mole percent.

TABLE 3 1223 Hours 1234yf 244bb 1233xd (2 isomers) Other 3 68.8 17.9 5.10.5 7.7 4 61.5 22.7 7.4 1.1 7.3 8 61.1 15.0 14.1 3.9 5.9 12 60.1 13.716.4 6.0 9.8 15 66.9 14.5 12.0 2.7 3.9 19 67.4 7.0 16.6 8.2 0.8

Example 5

Example 5 demonstrates the dehydrochlorination of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activatedcarbon catalyst.

An Inconel® tube (½ inch OD) was filled with 4 cc (1.99 gm) of acidwashed PCB Polynesian coconut shell based carbon from Calgon (6-10mesh). HFC-244bb was fed at 1.04 mL/hour through a vaporizer set at 40°C. using a N₂ sweep of 2.4 sccm (4.0×10⁻⁸ m³) giving a total contacttime of about 32 seconds while controlling the reactor temperature at400° C.

The data in Table 4 shows the reactor effluent composition in molepercent for this process run with an activated carbon catalyst to makeHFC-1234yf via HCl elimination over the period of 7 hours of operation.

TABLE 4 Hours 1234yf 244bb 1233xf Other 1 52.2 22.4 10.3 15.1 2 44.524.6 13.4 17.5 3 38.0 31.9 14.8 15.3 4 25.9 41.8 15.7 16.6 5 15.5 49.417.9 17.2 6 7.1 53.8 18.0 21.1 7 2.9 54.2 17.3 25.6

1. A composition comprising HFO-1234yf and at least one additionalcompound selected from the group consisting of HCO-1250xf, HCC-260da,HCC-260 db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb,HCFC-244 db, HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za,HCFO-1224zb, HFO-1225zc, HCFC-241 db, HCFC-242dc, HCFO-1232xf,HCFO-1231xf, and HCFO-1233yf.
 2. The composition of claim 1 comprisingHCFO-1232xf.
 3. The composition of claim 2 further comprising at leastone compound selected from the group consisting of HCFC-243 db,HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241 db.
 4. The compositionof claim 1 further comprising at least one compound selected from thegroup consisting of HCFC-243 db and HFC-245fa.
 5. The composition ofclaim 1 containing less than about 1 weight percent of said additionalcompound, based on the total weight of the composition.
 6. Thecomposition of claim 3 further comprising from about 1 ppm to about 1000ppm of HFC-245cb.
 7. A composition comprising HCO-1230xa and at leastone additional compound selected from the group consisting of propylene,HCO-1260zf, HCC-260da, HCC-260 db, HCO-1250xf, HCC-250aa, and HCC-240aa.8. The composition of claim 7 comprising HCC-240aa.
 9. The compositionof claim 8 further comprising at least one compound selected from thegroup consisting of HCC-250aa and HCC-260da.
 10. A compositioncomprising HCFO-1233xf and at least one additional compound selectedfrom the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa, HCC-240aa, HCO-1230xa, HFO-1243zf,HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1233yf, HCFO-1232xf,HCFC-1231xf, HCFC-241 db, and HCFC-242dc.
 11. The composition of claim10 comprising HCFO-1232xf.
 12. The composition of claim 11 furthercomprising HCFO-1231xf.
 13. A composition comprising HCFC-244bb and atleast one additional compound selected from the group consisting ofpropylene, HCO-1250xf, HCC-260da, HCC-260 db, HCC-240aa, HCO-1230xa,HCFO-1233xf, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFC-1233yf.
 14. Thecomposition of claim 13 further comprising at least one compoundselected from the group consisting of HCFC-243 db and HFC-245fa.
 15. Thecomposition of claim 10 further comprising HF.
 16. The composition ofclaim 10 that are acid free.
 17. A method for producing coolingcomprising evaporating a composition of claim 1 in the vicinity of abody to be cooled, and thereafter condensing said composition.
 18. Amethod for producing heat comprising condensing a composition of claim 1in the vicinity of a body to be heated, and thereafter evaporating saidcompositions.
 19. A method of forming a foam comprising: (a) adding to afoamable composition a composition of claim 1; and (b) processing thefoamable composition under conditions effective to form a foam.
 20. Aprocess for producing aerosol products comprising the step of adding acomposition of claim 1 to a formulation, including active ingredients inan aerosol container, wherein said composition functions as apropellant.